CN1704436A - Process for continuous solid phase grafting preparation of polyolefin and device therefor - Google Patents
Process for continuous solid phase grafting preparation of polyolefin and device therefor Download PDFInfo
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- CN1704436A CN1704436A CN 200410024794 CN200410024794A CN1704436A CN 1704436 A CN1704436 A CN 1704436A CN 200410024794 CN200410024794 CN 200410024794 CN 200410024794 A CN200410024794 A CN 200410024794A CN 1704436 A CN1704436 A CN 1704436A
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Abstract
The invention discloses a process and apparatus for continuous solid phase grafting preparation of polyolefin, wherein various raw materials are continuously charged into horizontal or vertical reactor with an agitator for reaction, then the procedures of reaction, scouring, filtering, and drying are carried out to obtain grafting modified polyolefin. The invention can realize good mixing effect and increased reaction efficiency, the grafting rate can reach over 1%.
Description
Technical field
The present invention relates to the manufacture of polyolefins technology, specifically, relate to polyolefine solid phase grafting production technique and equipment.
On main chain, introduce polar group after the polyolefine graft modification, can strengthen the interface binding intensity of polymkeric substance and mineral filler, improve the consistency of polymer blending alloy.
Polyolefinic graft-modification method mainly contains solution grafting, fusion-grafting method and solid phase grafting method etc.
Solution grafting can obtain higher percentage of grafting, but owing to will use a large amount of solvents, the aftertreatment complexity, environmental pollution is serious, and the cost height does not have competitive power;
Fusion graft process is simple, can realize serialization production, but percentage of grafting is relatively low, and polymer degradation is serious, and grafted products contains unreacted impurity such as monomer completely, the post-treatment product properties is produced have a strong impact on;
Solid phase grafting carries out graft reaction under the polymer glass transition temperature, temperature of reaction is low, need not or seldom uses solvent, and is easy to operate, product percentage of grafting height, and it is low suitably to handle rear impurity content, and facility investment is little, is a kind of up-and-coming grafting method.
Rengarajan etc. report the earliest and adopt the stainless steel reactor of adjustable speed Sigma type double leaf stirring rake to carry out polypropylene (PP) solid phase grafting that required reaction mass adds (Polymer, 1989,30:933 in batches; 1990,31:1703).U.S. Pat Patent 5,079, and 302 provide the solid phase grafting method of polyolefine when adding catalyzer or not adding catalyzer in detail, do not have the description about the reactor aspect.The solid phase grafting experimental installation of employings such as Subramanian is specially designed 4 blade stainless steel reactors, reaction volume 800ml, the interrupter method operation (J.Appl.Polym.Sci., 1998,70:1001).U.S. Pat Patent 5,585,435 disclose a kind of fluidized-bed reactor (vertical or horizontal) that stirs with band carries out the method that the cinnamic serialization of PP powder solid phase grafting is produced, with the powder fluidisation, the ethylbenzene and the initiator that feed gasification carry out grafting to this method with superheated vapour or superheated vapour/pure steam.Grafts is transported to post-reactor continuously and further removes unreacted reactant, enters twin screw extruder at last and adds stabilization aid and melt extrude granulation.
Pan Yongkang etc. have carried out solid phase grafting glycidyl methacrylate (GMA) in laboratory Haake40 changes on the Rheomix type Banbury mixer of rheometer and the TW100 conical double screw extruder, still do not have industrial application value (doctorate paper, 1997).
The technical issues that need to address of the present invention are to disclose continuous solid phase grafting production method of a kind of polyolefine and device, and to overcome the existing in prior technology fluctuation of service, percentage of grafting is low, particularly bad, the environmental pollution important disadvantages of product homogeneity.
Method of the present invention comprises the steps:
But polyolefine solid grafted monomer, interfacial agents, catalyzer and initiator are added continuously the horizontal or vertical reactor reaction that has agitator, through obtaining the polyolefine of graft modification after the operations such as reaction, washing, filtration, drying, the said agitator that reactor adopted that has agitator has inside and outside two ribbons that the hand of spiral is opposite, because this reactor has inside and outside two ribbons that the hand of spiral is opposite, therefore in the reaction process, the material direction of propulsion is opposite, very good mixing effect can be obtained, thereby reaction efficiency can be improved.
Said polyolefine comprises polypropylene, polyethylene and ethylene/propene copolymer;
Said grafted monomer comprises alkenyl monomer, and as unsaturated vinylformic acid of ethylene linkage or derivative, as acid anhydrides, ester, acid amides etc., preferred grafted monomer is maleic anhydride, vinylformic acid, acrylate, vinylbenzene or glycidyl methacrylate;
Said radical initiator comprises peroxide initiator, and as lauroyl peroxide or benzoyl peroxide, the transformation period is the organo-peroxide of 4-40min in the preferred 100-140 ℃ of scope.
Said interfacial agents is selected the organic solvent of energy corrosion or swollen polymer, preferred benzene,toluene,xylene or perhydronaphthalene.Preferably select toluene and dimethylbenzene for use.
Isocyanuric acid or the acid of cyanogen urea that said catalyzer selects the allyl group of energy stabilized radical to replace.
Monomer and initiator raw material can be sneaked in the polymkeric substance and be added, and also can add separately, and graft product can adopt conventional method to carry out purifying.
Because the present invention has adopted the reactor with the opposite ribbon of inside and outside two direction of propulsion, therefore, it is very crucial adopting suitable process conditions to guarantee to react, suitable reaction temperature is 100～140 ℃, stirring velocity is 80～150r/min, the residence time is 30～150min, powder filling rate 20～60%;
Weight ratio between polyolefine, monomer, initiator, interfacial agents, the catalyzer is:
1∶0.03～0.15∶0.03～0.13∶0～0.2∶0～0.1。
Adopt method of the present invention to carry out the polyolefine solid phase grafting, percentage of grafting can reach more than 1%, and is adapted to graft polyolefin homopolymer or multipolymer, has good uniformity, processing condition wide ranges, operation reliable characteristics.Even poor to flowability, adhesion each other, the solid that tends to move to wall also is suitable for.
Description of drawings
Fig. 1 is a process flow sheet.
Fig. 2 is the structure of reactor synoptic diagram.
Embodiment
Referring to Fig. 1, method of the present invention comprises the steps:
With polyolefine, grafted monomer, the superoxide that forms free radical mixes in mixer 1, be delivered to the reactor hopper by feeder 2, add reactor 5 continuously by screw feeder, interfacial agents in the solvent trough 3 and catalyzer enter reactor 5 by inlet separately, feed nitrogen and heating medium, various materials constantly mix in reactor, reaction, flow into medial launder 6 from the grafts outlet at last, water-filling suspends reaction product in the medial launder, be transported to washing still 7 heated scrubs after a certain amount of and remove impurity such as the unreacted monomer that may contain and initiator, behind whizzer 8 filter dehydrations, send again drying machine 10 dry products.
As seen from Figure 2, the present invention is used to realize that the device of described method comprises reactor, said reactor 5 comprises housing 501 at least and is arranged on rotating agitator 502 in the housing 501, said agitator 502 has outer ribbon 503 and interior ribbon 504, and outer ribbon 503 is opposite with interior ribbon 504 hands of spiral.
The outer ribbon 503 and interior ribbon 504 hands of spiral refer to " outer ribbon arranges that by left hand direction interior ribbon is arranged by the dextrorotation direction " on the contrary
Embodiment 1
Polypropylene powder, maleic anhydride, benzoyl peroxide are mixed in mixer in 10: 0.5: 0.5 ratios, add the ribbon stirred reactor by screw feeder continuously with the 11kg/h flow after being delivered to hopper, 0.8kg/h dimethylbenzene adds reactor after metering.Mixing speed is 100r/min, and the reactor content temperature is 110 ℃, by the heating of circulating heat conduction oil.Logical nitrogen protection in the reaction process.Reaction product enters the medial launder that band stirs continuously, and medial launder adds water 150kg.Behind the certain hour, the 250kg solidliquid mixture is delivered to the washing still, replenishes 100kg water, be heated to 50 ℃, stir half an hour.Then with the solidliquid mixture centrifuge dehydration, solid vacuum-drying.Output is 10.8kg/h, percentage of grafting 2.0%.Waste water recycles after water treatment device is removed impurity.
Embodiment 2
Polypropylene powder, maleic anhydride, benzoyl peroxide are mixed in mixer in 10: 1: 0.8 ratios, add the ribbon stirred reactor by screw feeder continuously with the 11.8kg/h flow after being delivered to hopper, 1kg/h dimethylbenzene and 0.5kg/h isocyanuric acid mix after be metered into reactor.Mixing speed is 110r/min, and the reactor content temperature is 120 ℃, by the heating of circulating heat conduction oil.Logical nitrogen protection in the reaction process.Reaction product enters the medial launder that band stirs continuously, and medial launder adds water 180kg.Behind the certain hour, the 300kg solidliquid mixture is delivered to the washing still, replenishes 80kg water, be heated to 70 ℃, stir half an hour.Then with the solidliquid mixture centrifuge dehydration, solid vacuum-drying.Output is 11.2kg/h, percentage of grafting 5.4%.Waste water recycles after water treatment device is removed impurity.
Embodiment 3
Polyethylene powder, maleic anhydride, benzoyl peroxide are mixed in mixer in 10: 0.3: 0.3 ratios, add the ribbon stirred reactor by screw feeder continuously with the 10.6kg/h flow after being delivered to hopper, 0.5kg/h dimethylbenzene adds reactor after metering.Mixing speed is 120r/min, and the reactor content temperature is 100 ℃, by the heating of circulating heat conduction oil.Logical nitrogen protection in the reaction process.Reaction product enters the medial launder that band stirs continuously, and medial launder adds water 200kg.Behind the certain hour, the 280kg solidliquid mixture is delivered to the washing still, replenishes 100kg water, be heated to 65 ℃, stir half an hour.Centrifuge dehydration then, vacuum-drying.Output is 10.5kg/h, percentage of grafting 1.7%.
Claims (10)
1. continuous solid phase grafting production method of polyolefine, it is characterized in that, comprise the steps: but polyolefine solid grafted monomer, interfacial agents, catalyzer and initiator are added the horizontal or vertical reactor reaction that has agitator continuously, adopt conventional method purification reaction product then, the said agitator that reactor adopted that has agitator has inside and outside two ribbons that the hand of spiral is opposite.
2. method according to claim 1 is characterized in that said polyolefine comprises polypropylene, polyethylene or ethylene/propene copolymer.
3. method according to claim 1 is characterized in that, said grafted monomer comprises a kind of in maleic anhydride, vinylformic acid, acrylate, vinylbenzene or the glycidyl methacrylate.
4. method according to claim 1 is characterized in that, said radical initiator is a peroxide initiator.
5. method according to claim 1 is characterized in that, said interfacial agents is selected from a kind of in benzene,toluene,xylene or the perhydronaphthalene.
6. method according to claim 1 is characterized in that, said catalyzer is isocyanuric acid or the acid of cyanogen urea.
7. method according to claim 1 is characterized in that, monomer and initiator raw material are sneaked into and added in the polymkeric substance or add separately.
8. according to each described method of claim 1～7, it is characterized in that temperature of reaction is 100～140 ℃, stirring velocity is 80～150r/min, and the residence time is 30～150min, powder filling rate 20～60%.
9. method according to claim 8 is characterized in that, the weight ratio between polyolefine, monomer, initiator, interfacial agents, the catalyzer is:
1∶0.03～0.15∶0.03～0.13∶0～0.2∶0～0.1。
10. be used to realize that each described square law device of claim 1～9 comprises reactor (5), it is characterized in that, said reactor (5) comprises housing (501) and is arranged on rotating agitator (502) in the housing (501), said agitator (502) has outer ribbon (503) and interior ribbon (504), and outer ribbon (503) is opposite with interior ribbon (504) hand of spiral.
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| CN 200410024794 CN1704436A (en) | 2004-05-31 | 2004-05-31 | Process for continuous solid phase grafting preparation of polyolefin and device therefor |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745361B (en) * | 2010-01-22 | 2013-03-13 | 扬州惠通化工技术有限公司 | High-viscosity self-cleaning reactor |
| CN104607132A (en) * | 2014-08-26 | 2015-05-13 | 南通赛孚机械设备有限公司 | Horizontal zinc stearate loop reaction kettle |
| CN105622850A (en) * | 2016-03-30 | 2016-06-01 | 北京海科华昌新材料技术有限公司 | Efficient and environment-friendly preparation method of double-monomer solid-phase grafted PP (polypropylene) |
| CN106288705A (en) * | 2016-08-18 | 2017-01-04 | 江西赛维Ldk光伏硅科技有限公司 | Dry agitator, processing system and the processing method of silicon tetrachloride slag slurry in cold hydrogenation process |
| CN107441983A (en) * | 2017-09-12 | 2017-12-08 | 云南云天化农业科技股份有限公司 | A kind of rabbling mechanism and with fertile equipment |
| WO2019206288A1 (en) | 2018-04-27 | 2019-10-31 | 中国石油化工股份有限公司 | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof |
| CN112940186A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院化学研究所 | Preparation method of polyolefin solid-phase grafted maleic anhydride |
-
2004
- 2004-05-31 CN CN 200410024794 patent/CN1704436A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745361B (en) * | 2010-01-22 | 2013-03-13 | 扬州惠通化工技术有限公司 | High-viscosity self-cleaning reactor |
| CN104607132A (en) * | 2014-08-26 | 2015-05-13 | 南通赛孚机械设备有限公司 | Horizontal zinc stearate loop reaction kettle |
| CN105622850A (en) * | 2016-03-30 | 2016-06-01 | 北京海科华昌新材料技术有限公司 | Efficient and environment-friendly preparation method of double-monomer solid-phase grafted PP (polypropylene) |
| CN106288705A (en) * | 2016-08-18 | 2017-01-04 | 江西赛维Ldk光伏硅科技有限公司 | Dry agitator, processing system and the processing method of silicon tetrachloride slag slurry in cold hydrogenation process |
| CN106288705B (en) * | 2016-08-18 | 2019-07-23 | 江西赛维Ldk光伏硅科技有限公司 | Drying blender, processing system and processing method for silicon tetrachloride slag slurry |
| CN107441983A (en) * | 2017-09-12 | 2017-12-08 | 云南云天化农业科技股份有限公司 | A kind of rabbling mechanism and with fertile equipment |
| WO2019206288A1 (en) | 2018-04-27 | 2019-10-31 | 中国石油化工股份有限公司 | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof |
| US11926687B2 (en) | 2018-04-27 | 2024-03-12 | China Petroleum & Chemical Corporation | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof |
| CN112940186A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院化学研究所 | Preparation method of polyolefin solid-phase grafted maleic anhydride |
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